Heterogeneous Effects on Chemo-Mechanical Coupling Behaviors at the Single-Particle Level

Understanding and alleviating the chemo-mechanical degradation of silicon anodes is a formidable challenge due to the large volume change during operations. Here, for a comprehensive understanding of heterogeneous effects on chemo-mechanical behaviors at the single-particle level, in situ observation of single-crystalline silicon micropillar electrodes under the inhomogeneous extrinsic conditions, taken as an example, was made. The observation shows that the anisotropic deformation patterns and fracture starting sites are reshaped with the combination of the inhomogeneous electrochemical driving force for charge transfer at the interface between the silicon micropillar and the electrolyte, and crystal orientation-dependent lithiation dynamics. Also, the numerical simulation unravels the underlying mechanisms of deformation and fracture behaviors, and well predicts the relative depth of lithiation at the time of crack initiation under heterogeneous conditions. The results show that heterogeneities arising from extrinsic conditions may induce inhomogeneous mechanical damage and tailor lithiation degree at an active particle level, offering insights into designing large-volume-change battery particles with good mechanical integrity and electrochemical performance under heterogeneous impacts.